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1.
The structure of catalysts based on vanadium oxide supported on different oxides (SiO2, γ-Al2O3, ZrO2, and TiO2) was investigated. Their catalytic properties in the selective oxidation of methanol in a temperature range of 100–250°C were studied. It was shown that the nature of the support determines the structure of the oxide forms of vanadium. The supporting of vanadium on SiO2 and γ-Al2O3 leads to the preferred formation of crystalline V2O5; the surface monomeric and polymeric forms of VOx are additionally formed on ZrO2 and TiO2. It was established that the crystalline V2O5 oxide is least active in the selective oxidation of methanol; the polymeric forms are more active than monomeric ones. The mechanism of the selective oxidation of methanol to dimethoxymethane and methyl formate on the vanadium oxide catalysts is considered.  相似文献   

2.
Stability of the Pd-, Co-, and Mn-zeolite catalysts supported on metal blocks was studied in high-temperature methane oxidation. The temperature regions were found in which the starting catalysts exhibit stable performance. The temperature was determined at which a partial deactivation is followed by stabilization of catalysts in reaction environment. In terms of specific activity, the partially deactivated Pd-zeolite catalyst is several times more active than conventional oxidation catalysts Pd/Al2O3, Pt/Al2O3, and the most active oxide CeO·6Al2O3.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2075–2078, October, 2004.  相似文献   

3.
The properties of the catalysts for partial oxidation of o-xylene depend on the structure of the supported vanadium sites. The structure itself is strongly dependent on the calcination temperature of the catalyst at which thermal deposition of the metal oxide on the oxide support takes place. We have investigated the effect of calcination temperature on the activity and selectivity of industrial V2O5-TiO2 (anatase) supported catalysts designed for partial oxidation of o-xylene in their application to methanol oxidation.This revised version was published online in December 2005 with corrections to the Cover Date.  相似文献   

4.
The partial oxidation of isobutylene to methacrolein on a multicomponent multiphase Co-Mo-Bi-Fe-Sb-K-O catalyst and on catalysts from which some components were absent was studied. Activity and selectivity changes in the case of isobutylene oxidation were the same as in the oxidation of propylene; however, the rate of propylene oxidation was higher than that of isobutylene oxidation. The X-ray diffraction analysis of the catalysts before and after the reaction indicated the occurrence of a number of phases in the samples: α-CoMoO4, β-CoMoO4, Fe2(MoO4)3, reduced bismuth molybdate species, MoO3, and reduced MoO x species. Under catalytic reaction conditions, redox phase transformations occurred. Iron molybdate and molybdenum oxide phases underwent the largest transformations. Of two molybdenum oxide phases, a β-Mo4O11 phase with a structure of a crystallographic shift is formed in the course of catalysis, whereas the second phase (MoO3) almost does not participate in catalysis and occurs in an excess.  相似文献   

5.
Modification of V2O5 with Ti, Sn, Zr, Nb, and Al oxides improves the activity and selectivity of the vanadium oxide catalyst in vapor-phase oxidation of β-picoline to give nicotinic acid. It is shown that the conversion of β-picoline and the yield of nicotinic acid on two-component V2O5-TiO2, V2O5-SnO2, V2O5-ZtrO2, V2O5-Nb2O5, and V2O5-Al2O3 catalysts may be several times those on the V2O5 catalyst. It was found that, on passing from V2O5 to double-component vanadium-containing catalysts, the proton affinity of active oxygen bonded to vanadium, calculated by the quantum-chemical method, grows simultaneously with the increase in the activity of the catalysts in the oxidation reaction.  相似文献   

6.
The catalytic partial oxidation of methane was studied over single channels of monolith catalysts Pt/PrCeZrO/α-Al2O3 and Pt/GdCeZrO/α-Al2O3 using the temporal analysis of products (TAP) and kinetic transients. Effects of catalyst composition, oxidation state, time offset between O2 and CH4 pulses on activity, selectivity and dynamics of product formation were elucidated. Realization of the direct pyrolysis-CH4 partial oxidation route was reliably established. This route is favored by optimum lattice/surface oxygen mobility and reactivity controlled by the dopant type (Gd, Pr) and oxidation state of the complex cerium/zirconium oxide.  相似文献   

7.
Various methods for the preparation of vanadium-phosphorus oxide (VPO) catalysts supported on aerosils A-300 and A-50 and TiO2 were studied: a traditional method (in an organic solvent under varying the support addition time, the nature of the reducing agent, and the degree of reduction of vanadium oxide) and barothermal and mechanochemical syntheses. With the use of XRD analysis, it was found that the composition of the resulting VPO phase depends on the time of support addition to the synthesis and the temperature of thermal treatment. Conditions for the formation of a supported phase of VOHPO4·0.5H2O, the precursor of the active component (VO)2P2O7, were determined. The presence of vanadium in an oxidation state of +4 was demonstrated using EPR and UV-VIS spectroscopy. The specific surface areas and pore structures of the synthesized catalysts were determined. The catalytic properties of samples in the reactions of n-butane oxidation in an excess of the hydrocarbon and oxidative ethane dehydrogenation were studied. It was found that, as compared with traditional bulk VPO catalysts, the use of the synthesized supported VPO catalysts made it possible to improve the process characteristics of n-butane oxidation and did not change these characteristics in the reaction of oxidative ethane dehydrogenation.  相似文献   

8.
Oxidative ammonolysis of 3(4)-methyl- and 3,4-dimethylpyridines using vanadium oxide catalyst doped with Cr2O3, SnO2, and ZrO2 was studied. The yields of nitriles and conversion of the starting compounds were found to depend on the CH-acidity of the latter in the gas phase. The possible mechanisms of the formation of pyridine-3,4-dicarboxylic acid imide at the oxidative ammonolysis of 3,4-dimethylpyridine was discussed. The relation between the activity of the modified catalysts and the proton affinity of the vanadyl oxygen calculated by the extended Hückel method was established.  相似文献   

9.
Vanadium oxide catalysts of the monolayer type have been prepared by means of chemisorption of vanadate(V)-anions from aqueous solutions and by chemisorption of gaseous V2O3(OH)4. Using Al2O3, Cr2O3, TiO2, CeO2 and ZrO2, catalysts with an approximately complete monomolecular layer of vanadium(V) oxide on the carrier oxides can be prepared, if temperature is not too high. Divalent metal oxides like CdO and ZnO may already form threedimensional surface vanadates at moderate temperature. The thermal stability of a monolayer catalyst is related to the parameter z/a, i. e. the ratio of the carrier cation charge to the sum of ionic radii of carrier cation and oxide anion. Thus, monolayer catalysts will be thermally stable only under the condition that z/a is not too high (aggregated catalyst) nor too small (ternary compound formation).  相似文献   

10.
Supported catalysts are among the most important classes of catalysts. They are typically prepared by wet‐chemical methods, such as impregnation or co‐precipitation. Here we disclose that dry ball milling of macroscopic metal powder in the presence of a support oxide leads in many cases to supported catalysts with particles in the nanometer size range. Various supports, including TiO2, Al2O3, Fe2O3, and Co3O4, and different metals, such as Au, Pt, Ag, Cu, and Ni, were studied, and for each of the supports and the metals, highly dispersed nanoparticles on supports could be prepared. The supported catalysts were tested in CO oxidation, where they showed activities in the same range as conventionally prepared catalysts. The method thus provides a simple and cost‐effective alternative to the conventionally used impregnation methods.  相似文献   

11.
Catalysts based on uranium oxides were systematically studied for the first time. Catalysts containing various amounts of uranium oxides (5 and 15%) supported on alumina and mixed Ni-U/Al2O3 catalysts were synthesized. The uranium oxide catalysts were characterized using the thermal desorption of argon, the low-temperature adsorption of nitrogen, X-ray diffraction analysis, and temperature-programmed reduction with hydrogen and CO. The effects of composition, preparation conditions, and thermal treatment on physicochemical properties and catalytic activity in the reactions of methane and butane oxidation, the steam and carbon dioxide reforming of methane, and the partial oxidation of methane were studied. It was found that a catalyst containing 5% U on alumina calcined at 1000°C was most active in the reaction of high-temperature methane oxidation. For the Ni-U/Al2O3 catalysts containing various uranium amounts (from 0 to 30%), the introduction of uranium as a catalyst constituent considerably increased the catalytic activity in methane steam reforming and partial oxidation.  相似文献   

12.
The physicochemical properties of V2O5/Al2O3 and MgO–V2O5/Al2O3 supported catalysts (Mg : V = 1 : 1, 2 : 1, and 3 : 2) obtained by consecutive impregnation of the support with solutions of vanadium and magnesium precursors are studied using a complex of mutually complementary methods (XRD, Raman spectroscopy, UV–Vis spectrometry, and TPR-H2). The effect of the formation of surface magnesium vanadates of various composition and structure on the catalytic properties of the supported vanadium oxide catalysts in the oxidative dehydrogenation of propane is studied. The introduction of magnesium in the samples and an increase in its content, accompanied by a change in the structure of the surface vanadium oxide phases from polymeric VO6/VO5 species to surface metavanadate species, magnesium metavanadate, and further to magnesium divanadate, significantly affects their catalytic properties in the reaction of the oxidative dehydrogenation of propane to propylene.  相似文献   

13.
The acid-base character of vanadium pentoxide, V2O5/SiO2 and V2O5/γ-Al2O3 catalysts has been investigated by adsorption of ammonia and sulphur dioxide using microcalorimetry. By depositing vanadium oxide on silica; new surface sites are formed which present more acid strength than bulk vanadium pentoxide and pure silica. Alumina-supported vanadium catalysts can be regarded as acidic monolayers VOx. Sulphur dioxide was found to be selective for uncovered alumina.  相似文献   

14.
A magnetically recyclable vanadium(V) catalyst was synthesized by covalent anchoring of VO(salen)Cl on silica-coated Fe3O4 nanoparticles. This straightforward preparation yields magnetically separable Fe3O4@SiO2@VO(salen) nanoparticles with high vanadium loading. These nanoparticles were efficient catalysts for selective oxidation of sulfides to corresponding sulfoxides with urea hydrogen peroxide in excellent yields. Leaching and recycling experiments revealed that the nanocatalyst can be applied for nearly complete oxidation of sulfides for at least five successive cycles.  相似文献   

15.
Catalytic CO oxidation by molecular O2 is an important model reaction in both the condensed phase and gas‐phase studies. Available gas‐phase studies indicate that noble metal is indispensable in catalytic CO oxidation by O2 under thermal collision conditions. Herein, we identified the first example of noble‐metal‐free heteronuclear oxide cluster catalysts, the copper–vanadium bimetallic oxide clusters Cu2VO3–5? for CO oxidation by O2. The reactions were characterized by mass spectrometry, photoelectron spectroscopy, and density functional calculations. The dynamic nature of the Cu?Cu unit in terms of the electron storage and release is the driving force to promote CO oxidation and O2 activation during the catalysis.  相似文献   

16.
A series of 1, 3, and 5% Bi-doped vanadium phosphate catalyst catalysts were prepared via sesquihydrate route using direct ultrasound method and were denoted as VPSB1, VPSB3, and VPSB5, respectively. These catalysts were synthesized solely using a direct ultrasound technique and calcined in a n-butane/air mixture. This study showed that catalyst synthesis time can be drastically reduced to only 2 hr compared to conventional 32–48 hr. All Bi-doped catalysts exhibited a well-crystallized (VO)2P2O7 phase. In addition, two V5+ phases, that is, β-VOPO4 and αII-VOPO4, were observed leading to an increase in the average oxidation state of vanadium. All catalysts showed V2p3/2 at approx. 517 eV, giving the vanadium oxidation state at approx. 4.3–4.6. Field-emission scanning electron microscopy micrographs showed the secondary structure consisting of thin and small plate-like crystal clusters due to the cavitation effect of ultrasound waves. VPSB5 showed the highest amount of oxygen species removed associated with the V5+ and V4+ species in temperature-programmed reduction in H2 analyses. TheX-ray absorption near edge structure (XANES) measurement showed the occurrence of vanadium oxide reductions in hydrogen gas flow, indicating the presence of V4+ and V5+ species. Higher average valence states of V5+, indicating more V5+ phases, were present. The addition of bismuth has increased the activity and selectivity to maleic anhydride.  相似文献   

17.
The vapor phase oxidation of 2-ethylhexanal over a series of oxide catalysts has been studied at 373–623 K. Monolayer vanadia supported on SiO2 and TiO2, molybdena and tungstenia supported on SiO2, and SnO2 were used as the catalysts. In contrast to the liquid phase process, resulting in 2-ethylhexanoic acid, the main observed reaction was reactant combustion. The partial oxidation products were 3-heptanone, 3-heptyl formate, and heptene. No traces of 2-ethylhexanoic acid were detected in any of the transformations performed.  相似文献   

18.
Ce0.46Zr0.54O2 solid solution prepared using a cellulose template was employed as a carrier for vanadium catalysts of the oxidative dehydrogenation of propane. The properties of VO х /Ce0.46Zr0.54O2 catalyst (5 wt % vanadium) are compared with the properties of the neat support. The carrier and catalyst are studied by means of BET, SEM, DTA, XRD, and Raman spectroscopy. It is shown that the CeVO4 phase responsible for the ODH process is formed upon interaction between vanadate ions and cerium ions on the surface of the solid solution. The catalytic properties of the catalyst and the support are studied in the propane oxidation reaction at temperatures of 450 and 500°C with pulse feeding of the reagent. It is found that the complete oxidation of propane occurs on the support with formation of CO2 and H2O. Three products (propene, CO2, and H2O) form in the presence of the vanadium catalyst. It is suggested that there are two types of catalytic centers on the catalyst’s surface. It is concluded that the centers responsible for the complete oxidation of propane are concentrated mainly on the carrier, while the centers responsible for propane ODH are on the CeVO4.  相似文献   

19.
A series of TiO2?CZrO2 supported V2O5 catalysts with vanadia loadings ranging from 4 to 12 wt% were synthesized by a wet impregnation technique and subjected to various thermal treatments at temperatures ranging from 773 to 1,073?K to understand the dispersion and thermal stability of the catalysts. The prepared catalysts were characterized by X-ray powder diffraction (XRD), BET surface area, oxygen uptake, and X-ray photoelectron spectroscopy (XPS) techniques. XRD results of 773?K calcined samples conferred an amorphous nature of the mixed oxide support and a highly dispersed form of vanadium oxide. Oxygen uptake measurements supported the formation of a monolayer of vanadium oxide over the thermally stable TiO2?CZrO2 support. The O 1s, Ti 2p, Zr 3d, and V 2p core level photoelectron peaks of TiO2?CZrO2 and V2O5/TiO2?CZrO2 catalysts are sensitive to the calcination temperature. No significant changes in the oxidation states of Ti4+ and Zr4+ were noted with increasing thermal treatments. Vanadium oxide stabilized as V4+ at lower temperatures, and the presence of V5+ is observed at 1,073?K. The synthesized catalysts were evaluated for selective oxidation of o-xylene under normal atmospheric pressure in the temperature range of 600?C708?K. The TiO2?CZrO2 support exhibits very less conversion of o-xylene, while 12 wt% V2O5 loaded sample exhibited a good conversion and a high product selectivity towards the desired product, phthalic anhydride.  相似文献   

20.
The effect of the carrier on catalytic properties of ruthenium supported catalysts in partial oxidation of methane (POM) was investigated. A variety of supports differed in texture and reducibility (Al2O3, SiO2, TiO2, Cr2O3, CeO2 and Fe2O3) were used. The catalyst activity is governed by ruthenium phase formation (RuO2 → Ru0), and it depends on redox properties of the support as well as support-ruthenium phase interaction. The activity of Ru supported catalysts decreases in the order Al2O3 ≈ SiO2 > Cr2O3 > TiO2 > CeO2 > Fe2O3. No significant effects of the specific surface area and porosity of catalysts on the methane conversion and selectivity of CO formation were found. The selectivity of CO2 formation (total oxidation of CH4) under conditions of POM (a ratio of CH4/O2 = 2) is associated with the contribution of reducible support oxides into the catalytic performance.  相似文献   

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